Thioamides and their use as crop protection agents

ABSTRACT

Thioamides of the formula I ##STR1## where A, B, R&#39; are hydrogen, cyano, alkyl, alkoxy or halogen, 
     X is ═CHCH 3  or ═N--OCH 3 , 
     R 1 , R 2  are hydrogen or alkyl, 
     Y is a group --O--, --S--, ##STR2##  --O--CH 2 , --CH 2  --O--, --S--CH 2  --, --CH 2  --S--, --CH 2  --CH 2 , --CH═CH--, --C.tbd.C-- or --CH 2  --O--N═C(R&#39;)-- and 
     R is hydrogen, unsubstituted or substituted alkyl, unsubstituted substituted or substituted cycloalkyl, unsubstituted or substituted aryl or unsubstituted or substituted hetaryl, and pesticides containing these compounds.

This is a Division of application Ser. No. 08/158,390 filed on Nov. 29,1993 now U.S. Pat. No. 5,393,782.

The present invention relates to novel thioamides, methods of preparingthem, and methods for combatting pests, especially fungi, insects,nematodes and mites, with these compounds.

It is known that certain thiocarbamates (EP 432,503) and certainphenylacetamides (cf. EP 477,631 and 398,692) have a fungicidal orinsecticidal action. However, their action is unsatisfactory.

We have now surprisingly found that novel thioamides of the formula I##STR3## where A, B, R' are identical or different and each is hydrogen,cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen,

X is ═CHCH₃ or ═N--OCH₃,

R¹, R² are hydrogen or C₁ -C₄ -alkyl,

Y is a group --O--, --S--, ##STR4## --O--CH₂, --CH₂ --O--, --S--CH₂ --,--CH₂ --S--, --CH₂ --CH₂, --CH═CH--, --C.tbd.C-- or --CH₂ --O--N═C(R')--and

R is hydrogen, unsubstituted or substituted C₁ -C₁₀ -alkyl,unsubstituted or substituted C₁ -C₆ -cycloalkyl, unsubstituted orsubstituted aryl or unsubstituted or substituted hetaryl, the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen, cyano, CO₂ (C₁ -C₄ -alkyl), C(O)(C₁ -C₄ -alkyl), nitro, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoximino-C₁ -C₄-alkyl, aryl, aryloxy, benzyloxy, hetaryl, hetaryloxy or C₃ -C₆-cycloalkyl and the term "hetaryl" denoting an unsubstituted orsubstituted aromatic, mono-, di- or trinuclear five-membered orsix-membered heterocycle, have an excellent fungicidal, insecticidal,nematicidal and acaricidal action.

The radicals stated in formula I may for example have the followingmeanings:

A, B, R' may be hydrogen, cyano, C₁ -C₄ -alkyl (e.g., methyl), C₁ -C₄-alkoxy (e.g., methoxy) or halogen (fluoro, chloro, bromo, iodo),

X may be ═CHCH₃ or ═N--OCH₃,

R¹, R² may be hydrogen or C₁ -C₄ -alkyl (e.g., methyl, ethyl)

Y is a group --O--, --S--, ##STR5## --O--CH₂, --CH₂ --O--, --S--CH₂ --,--CH₂ --S--, --CH₂ -CH₂, --CH═CH--, --C.tbd.C-- or --CH₂ --O--N═C(R')--and

R may be hydrogen, unsubstituted or substituted C₁ -C₁₀ -alkyl (e.g.,methyl, ethyl, n-, isopropyl, n-, iso-, s-, tert. -butyl,trifluoromethyl, cyanomethyl, benzyl, methoxymethyl), unsubstituted orsubstituted C₁ -C₆ -cycloalkyl (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyctohexyl, 1-methylcyclopropyl), unsubstituted orsubstituted aryl (e.g., phenyl, 2-methylphenyl, 3-methoxyphenyl, 4-tert.-butoxyphenyl, naphthyl, 1-methyl-2-naphthyl), unsubstituted orsubstituted hetaryl (e.g., pyridinyl, 6-Cl-pyridin-2-yl, thiazolyl,2-benzthiazolyl, furyl, 2-furyl, pyrimidinyl, 4-pyrimidinyl), the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen (e..g, fluoro, chloro, bromo, iodo), cyano, CO₂ (C₁ -C₄ -alkyl)(e.g., CO₂ Me, CO₂ Et), C(O)(C₁ -C₄ -alkyl) (e.g., C(O)CH₃), nitro, C₁-C₄ -alkyl (e.g., methyl, ethyl, n-, isopropyl, n-, i-,s-, tert.-butyl),C₁ -C₄ -alkoxy (e.g., methoxy, ethoxy, n-, isopropoxy, n-, i-, s-,tert.-butoxy), C₁ -C₄ -haloalkyl (e.g., chloromethyl, bromomethyl,trifluoromethyl, 1,1,2,2-tetrafluoroethyl), C₁ -C₄ -alkoximino-C₁ -C₄-alkyl (e.g., methoximinomethyl, ethoximinomethyl, n-,isopropoximinomethyl, n-, i-, s-, tert. -butoximinomethyl,methoximinoethyl), aryl (e.g., phenyl, 1-, 2-naphthyl), aryloxy(phenoxy, 2-naphthyloxy), benzyloxy, hetaryl (e.g., pyridyl,pyrimidinyl, pyridazinyl, quinolinyl, furyl, thienyl, oxazolyl,isoxazolyl, benzthiazolyl, benzthienyl, benzoxazolyl, pyrryl),hetaryloxy (e.g., 2-pyridinyloxy, 2-quinolinyloxy, 4-pyrimidinyloxy), C₃-C₆ -cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl)and the term "hetaryl" denoting an unsubstituted or substituted aromaticmono-, di- or trinuclear five-membered or six-membered heterocycle(e.g., pyridine, quinoline, pyrimidine, benzthiazole, benzoxazole).

Preferred compounds of the formula I ##STR6## are those in which A, B,are hydrogen,

X is ═N--OMe,

R¹ is hydrogen,

R² is methyl,

and Y, R' and R have the meanings given in claim 1.

The novel compounds of the formula I may, because of the C═C-- or C═N--double bonds, be obtained as E/Z isomer mixtures. These may be separatedinto their individual components in conventional manner, e.g.,crystallization or chromatography. Both the individual isomericcompounds and mixtures thereof are encompassed by the invention and canbe used as pesticides.

The thioamides of the formula I are prepared for example by reactingamides of the formula II in conventional manner (cf. e.g., Houben-Weyl,vol. IX, pp. 764 et seq.) with a sulfurizing agent such as P₄ S₁₀ orLawesson's reagent ##STR7## The amides II are known or can be preparedby analogy to known methods (cf. EP 477631, 398692, 463488). Thepreparation of the compounds is illustrated by the following examples.

EXAMPLE 1

Preparation of 2-methoximino-2- 2'-(o-methylphenoxymethyl)-phenyl!acetic acid-N-methylthioamide (compound2, Table 1).

5 g (16 mmol) of 2-methoximino-2-2'-(o-methylphenoxymethyl)-phenyl!acetic acid-N-methylamide (disclosedin EP 477631) and 8.1 g (20 mmol) of Lawesson's reagent are refluxed for90 minutes in 50 ml of xylene. The solvent is then removed under reducedpressure. The residue was chromatographed twice on silica gel usingmixtures of hexane and methyl tert-butyl ether, and 1.7 g (32%) of thecompound was obtained as a yellow oil.

¹ H-NMR (CDCl₃ /TMS): δ=2.25 (CH₃); 3.21 (d, NHCH₃), 3.95 (OCH₃); 4.97(CH₂); 6.79-7.55 (aryl, 8 H); 8.57 (NH).

The compounds listed in the tables below may be obtained analogously:

                                      TABLE 1    __________________________________________________________________________     ##STR8##                                           Phys. data m. p.  °C.!    No.       Y           R.sup.1                      R.sup.2                         R                 IR  cm.sup.-1 ! H-NMR    __________________________________________________________________________                                            ppm!    1  CH.sub.2 O  Me H  phenyl    2  CH.sub.2 O  Me H  2-Me-phenyl       3360, 2940, 1595, 1520,                                           1494, 1241, 1228, 1122,                                           1052, 1025, 929, 752    3  CH.sub.2 O  Me H  3-Me-phenyl    4  CH.sub.2 O  Me H  4-Me-phenyl    5  CH.sub.2 O  Me H  2-Cl-phenyl    6  CH.sub.2 O  Me H  3-Cl-phenyl    7  CH.sub.2 O  Me H  4-Cl-phenyl    8  CH.sub.2 O  Me H  2-F-phenyl    9  CH.sub.2 O  Me H  3-F-phenyl    10 CH.sub.2 O  Me H  4-F-phenyl    11 CH.sub.2 O  Me H  2-Br-phenyl    12 CH.sub.2 O  Me H  3-Br-phenyl    13 CH.sub.2 O  Me H  4-Br-phenyl    14 CH.sub.2 O  Me H  2-OCH.sub.3 -phenyl    15 CH.sub.2 O  Me H  3-OCH.sub.3 -phenyl    16 CH.sub.2 O  Me H  4-OCH.sub.3 -phenyl    17 CH.sub.2 O  Me H  2-CF.sub.3 -phenyl    18 CH.sub.2 O  Me H  3-CF.sub.3 -phenyl    19 CH.sub.2 O  Me H  4-CF.sub.3 -phenyl    20 CH.sub.2 O  Me H  2-CO.sub.2 Me-phenyl    21 CH.sub.2 O  Me H  3-CO.sub.2 Me-phenyl    22 CH.sub.2 O  Me H  4-CO.sub.2 Me-phenyl    23 CH.sub.2 O  Me H  2,3-Me.sub.2 -phenyl    24 CH.sub.2 O  Me H  2,4-Me.sub.2 -phenyl    25 CH.sub.2 O  Me H  2,5-Me.sub.2 -phenyl                                           3360, 2935, 1583, 1519,                                           1509, 1458, 1358, 1262,                                           1154, 1130, 1026    26 CH.sub.2 O  Me H  2,6-Me.sub.2 -phenyl    27 CH.sub.2 O  Me H  3,4-Me.sub.2 -phenyl    28 CH.sub.2 O  Me H  3,5-Me.sub.2 -phenyl    29 CH.sub.2 O  Me H  2,3-Cl.sub.2 -phenyl    30 CH.sub.2 O  Me H  2,4-Cl.sub.2 -phenyl    31 CH.sub.2 O  Me H  2,5-Cl.sub.2 -phenyl    32 CH.sub.2 O  Me H  2,6-Cl.sub.2 -phenyl    33 CH.sub.2 O  Me H  3,4-Cl.sub.2 -phenyl    34 CH.sub.2 O  Me H  3,5-Cl.sub.2 -phenyl    35 CH.sub.2 O  Me H  2-Cl, 4-Me-phenyl    36 CH.sub.2 O  Me H  2-Cl, 5-Me-phenyl    37 CH.sub.2 O  Me H  2-Me, 4-Cl-phenyl    38 CH.sub.2 O  Me H  2-Me, 5-Cl-phenyl    39 CH.sub.2 O  Me H  2-pyridyl    40 CH.sub.2 O  Me H  3-pyridyl    41 CH.sub.2 O  Me H  4-pyridyl    42 CH.sub.2 O  Me H  6-Cl-2-pyridyl    43 CH.sub.2 O  Me H  6-OCH.sub.3 -2-pyridyl    44 CH.sub.2 O  Me H  6-Me-2-pyridyl    45 CH.sub.2 O  Me H  5-CF.sub.3 -2-pyridyl    46 CH.sub.2 O  Me H  2-quinolyl    47 CH.sub.2 O  Me H  3-Me-2-quinolyl    48 CH.sub.2 O  Me H  8-Me-2-quinolyl    49 CH.sub.2 O  Me H  2-pyrimidinyl    50 CH.sub.2 O  Me H  4-CF.sub.3 -2-pyrimidinyl    51 CH.sub.2 O  Me H  benzothiazol-2-yl    52 CH.sub.2 O  Me H  5-Cl-benzothiazol-2-yl    53 CH.sub.2 O  Me H  6-Cl-benzothiazol-2-yl    54 CH.sub.2 O  Me H  2-Me-4-methoximinomethyl-phenyl                                           2.18; 2.27(CH.sub.3); 3.24                                           (d, NHCH.sub.3); 3.96; 3.97                                           (OCH.sub.3); 4.98(CH.sub.2);                                           6.79-7.51(Aryl, 7H); 8.61                                           ppm (NH).    55 CH.sub.2 O  Me H  2-Me-5-methoximinomethyl-phenyl    56 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-methoximinomethyl-phenyl    57 CH.sub.2 O  Me H  2-Me-4-ethoximinomethyl-phenyl    58 CH.sub.2 O  Me H  2-Me-5-ethoximinomethyl-phenyl    59 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-ethoximinomethyl-phenyl    60 CH.sub.2 O  Me H  2-Me-4-n-butoximinomethyl-phenyl    61 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-n-butoximinomethyl-phenyl    62 CH.sub.2 O  Me H  2-Me-4-allyloximinomethyl-phenyl    63 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-Allyloximinomethyl-phenyl    64 CH.sub.2 O  Me H  1-naphthyl    65 CH.sub.2 O  Me H  2-naphthyl    66 CH.sub.2 O  Me H  1-methyl-2-naphthyl    67 CH.sub.2 O  Me H  methyl    68 OCH.sub.2   Me H  H    69 OCH.sub.2   Me H  phenyl    70 OCH.sub.2   Me H  2-Cl-phenyl    71 CH.sub.2 S  Me H  2-Me-phenyl    72 CH.sub.2 S  Me H  Me    73 CH.sub.2 S  Me H  phenyl    74 CH.sub.2 S  Me H  2-Me-phenyl    75 CH.sub.2 S  Me H  2,5-Cl.sub.2 -phenyl    76 CH.sub.2 S  Me H  2-pyridyl    77 CH.sub.2 S  Me H  6-Cl-2-pyridyl    78 CH.sub.2 S  Me H  benzothiazol-2-yl    79 CH.sub.2 S  Me H  5-Cl-benzothiazol-2-yl    80 CH.sub.2 S  Me H  6-Cl-benzothiazol-2-yl    81 O           Me H  phenyl    82 O           Me H  2-naphthyl    83 O           Me H  2-Me-phenyl    84 O           Me H  3-Me-phenyl    85 O           Me H  4-Me-phenyl    86 O           Me H  2-Cl-phenyl    87 O           Me H  3-Cl-phenyl    88 O           Me H  4-Cl-phenyl    89 O           Me H  3-phenoxy-phenyl    90 O           Me H  6-(2-CN-phenoxy)-pyrimidin-4-yl    91 O           Me H  2-pyridyl    92 CC          Me H  phenyl    93 CC          Me H  2-Me-phenyl    94 CC          Me H  3-Me-phenyl    95 CC          Me H  4-Me-phenyl    96 CC          Me H  2-Cl-phenyl    97 CC          Me H  2,5-Me.sub.2 -phenyl    98        ##STR9##   Me H  phenyl    99        ##STR10##  Me H  2-Me-phenyl    100        ##STR11##  Me H  3-Me-phenyl    101        ##STR12##  Me H  4-Me-phenyl    102        ##STR13##  Me H  2-Cl-phenyl    103        ##STR14##  Me H  3-Cl-phenyl    104        ##STR15##  Me H  4-Cl-phenyl    104        ##STR16##  Me H  2-F-phenyl    105        ##STR17##  Me H  3-F-phenyl    106        ##STR18##  Me H  4-F-phenyl    107        ##STR19##  Me H  2-Br-phenyl    108        ##STR20##  Me H  3-Br-phenyl    109        ##STR21##  Me H  4-Br-phenyl    110        ##STR22##  Me H  2-CF.sub.3 -phenyl    111        ##STR23##  Me H  3-CF.sub.3 -phenyl    112        ##STR24##  Me H  4-CF.sub.3 -phenyl    113        ##STR25##  Me H  2-OCH.sub.3 -phenyl    114        ##STR26##  Me H  3-OCH.sub.3 -phenyl    115        ##STR27##  Me H  4-OCH.sub.3 -phenyl    116        ##STR28##  Me H  2-CO.sub.2 Me-phenyl    117        ##STR29##  Me H  3-CO.sub.2 Me-phenyl    118        ##STR30##  Me H  4-CO.sub.2 Me-phenyl    119        ##STR31##  Me H  2,3-Me.sub.2 -phenyl    120        ##STR32##  Me H  2,4-Me.sub.2 -phenyl    121        ##STR33##  Me H  2,5-Me.sub.2 -phenyl    122        ##STR34##  Me H  2,6-Me.sub.2 -phenyl    123        ##STR35##  Me H  3,4-Me.sub.2 -phenyl    124        ##STR36##  Me H  3,5-Me.sub.2 -phenyl    125        ##STR37##  Me H  2,3-Cl.sub.2 -phenyl    126        ##STR38##  Me H  2,4-Cl.sub.2 -phenyl    127        ##STR39##  Me H  2,5-Cl.sub.2 -phenyl    128        ##STR40##  Me H  2,6-Cl.sub.2 -phenyl    129        ##STR41##  Me H  3,4-Cl.sub.2 -phenyl    130        ##STR42##  Me H  3,5-Cl.sub.2 -phenyl                                           3360, 1583, 1556, 1518, 1409,                                           1358, 1304, 102, 856, 834, 800                                           cm.sup.-1.    131        ##STR43##  Me    2-Cl, 4-Me-phenyl    132        ##STR44##  Me H  2-Cl, 5-Me-phenyl    133        ##STR45##  Me H  2-Me, 4-Cl-phenyl    134        ##STR46##  Me H  2-Me, 5-Cl-phenyl    135        ##STR47##  Me H  2-pyridyl    136        ##STR48##  Me H  2-naphthyl    137        ##STR49##  Me H  1-Me-2-naphthyl    138        ##STR50##  Me H  2-furyl    139       CH.sub.2O   Me Me phenyl    140       CH.sub.2O   Et H  phenyl    141       CH.sub.2O   Et Et phenyl    __________________________________________________________________________

                                      TABLE 2    __________________________________________________________________________     ##STR51##                                            Phys. data m.p.  °C.!    No.       Y           R.sup.1                      R.sup.2                         R                  IR  cm.sup.-1 ! H-NMR    __________________________________________________________________________                                             ppm!    1  CH.sub.2 O  Me H  phenyl    2  CH.sub.2 O  Me H  2-Me-phenyl    3  CH.sub.2 O  Me H  3-Me-phenyl    4  CH.sub.2 O  Me H  4-Me-phenyl    5  CH.sub.2 O  Me H  2-Cl-phenyl    6  CH.sub.2 O  Me H  3-Cl-phenyl    7  CH.sub.2 O  Me H  4-Cl-phenyl    8  CH.sub.2 O  Me H  2-F-phenyl    9  CH.sub.2 O  Me H  3-F-phenyl    10 CH.sub.2 O  Me H  4-F-phenyl    11 CH.sub.2 O  Me H  2-Br-phenyl    12 CH.sub.2 O  Me H  3-Br-phenyl    13 CH.sub.2 O  Me H  4-Br-phenyl    14 CH.sub.2 O  Me H  2-OCH.sub.3 -phenyl    15 CH.sub.2 O  Me H  3-OCH.sub.3 -phenyl    16 CH.sub.2 O  Me H  4-OCH.sub.3 -phenyl    17 CH.sub.2 O  Me H  2-CF.sub.3 -phenyl    18 CH.sub.2 O  Me H  3-CF.sub.3 -phenyl    19 CH.sub.2 O  Me H  4-CF.sub.3 -phenyl    20 CH.sub.2 O  Me H  2-CO.sub.2 Me-phenyl    21 CH.sub.2 O  Me H  3-CO.sub.2 Me-phenyl    22 CH.sub.2 O  Me H  4-CO.sub.2 Me-phenyl    23 CH.sub.2 O  Me H  2,3-Me.sub.2 -phenyl    24 CH.sub.2 O  Me H  2,4-Me.sub.2 -phenyl    25 CH.sub.2 O  Me H  2,5-Me.sub.2 -phenyl    26 CH.sub.2 O  Me H  2,6-Me.sub.2 -phenyl    27 CH.sub.2 O  Me H  3,4-Me.sub.2 -phenyl    28 CH.sub.2 O  Me H  3,5-Me.sub.2 -phenyl    29 CH.sub.2 O  Me H  2,3-Cl.sub.2 -phenyl    30 CH.sub.2 O  Me H  2,4-Cl.sub.2 -phenyl    31 CH.sub.2 O  Me H  2,5-Cl.sub.2 -phenyl    32 CH.sub.2 O  Me H  2,6-Cl.sub.2 -phenyl    33 CH.sub.2 O  Me H  3,4-Cl.sub.2 -phenyl    34 CH.sub.2 O  Me H  3,5-Cl.sub.2 -phenyl    35 CH.sub.2 O  Me H  2-Cl-, 4-Me-phenyl    36 CH.sub.2 O  Me H  2-Cl-, 5-Me-phenyl    37 CH.sub.2 O  Me H  2-Me-, 4-Cl-phenyl    38 CH.sub.2 O  Me H  2-Me-, 5-Cl-phenyl    39 CH.sub.2 O  Me H  2-pyridyl    40 CH.sub.2 O  Me H  3-pyridyl    41 CH.sub.2 O  Me H  4-pyridyl    42 CH.sub.2 O  Me H  6-Cl-2-pyridyl    43 CH.sub.2 O  Me H  6-OCH.sub.3 -2-pyridyl    44 CH.sub.2 O  Me H  6-Me-2-pyridyl    45 CH.sub.2 O  Me H  5-CF.sub.3 -2-pyridyl    46 CH.sub.2 O  Me H  2-quinolyl    47 CH.sub.2 O  Me H  3-Me-2-quinolyl    48 CH.sub.2 O  Me H  8-Me-2-quinolyl    49 CH.sub.2 O  Me H  2-pyrimidinyl    50 CH.sub.2 O  Me H  4-CF.sub.3 -2-pyrimidinyl    51 CH.sub.2 O  Me H  benzothiazol-2-yl    52 CH.sub.2 O  Me H  5-Cl-benzothiazol-2-yl    53 CH.sub.2 O  Me H  6-Cl-benzothiazol-2-yl    54 CH.sub.2 O  Me H  2-Me-4-methoximinoethyl-1-phenyl    55 CH.sub.2 O  Me H  2-Me-5-methoximinomethyl-phenyl    56 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-methoximinomethyl-phenyl    57 CH.sub.2 O  Me H  2-Me-4-ethoximinomethyl-phenyl    58 CH.sub.2 O  Me H  2-Me-5-ethoximinomethyl-phenyl    59 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-ethoximinomethyl-phenyl    60 CH.sub.2 O  Me H  2-Me-4-n-butoximinomethyl-phenyl    61 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-n-butoximinomethyl-phenyl    62 CH.sub.2 O  Me H  2-Me-4-allyloximinomethyl-phenyl    63 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-allyloximinomethyl-phenyl    64 CH.sub.2 O  Me H  1-naphthyl    65 CH.sub.2 O  Me H  2-naphthyl    66 CH.sub.2 O  Me H  1-methyl-2-naphthyl    67 CH.sub.2 O  Me H  methyl    68 OCH.sub.2   Me H  H    69 OCH.sub.2   Me H  phenyl    70 OCH.sub.2   Me H  2-Cl-phenyl    71 OCH.sub.2   Me H  2-Me-phenyl    72 CH.sub.2 S  Me H  Me    73 CH.sub.2 S  Me H  phenyl    74 CH.sub.2 S  Me H  2-Me-phenyl    75 CH.sub.2 S  Me H  2,5-Cl.sub.2 -phenyl    76 CH.sub.2 S  Me H  2-pyridyl    77 CH.sub.2 S  Me H  6-Cl-2-pyridyl    78 CH.sub.2 S  Me H  benzothiazol-2-yl    79 CH.sub.2 S  Me H  5-Cl-benzothiazol-2-yl    80 CH.sub.2 S  Me H  6-Cl-benzothiazol-2-yl    81 O           Me H  phenyl    82 O           Me H  2-naphthyl    83 O           Me H  2-Me-phenyl    84 O           Me H  3-Me-phenyl    85 O           Me H  4-Me-phenyl    86 O           Me H  2-Cl-phenyl    87 O           Me H  3-Cl-phenyl    88 O           Me H  4-Cl-phenyl    89 O           Me H  3-phenoxy-phenyl    90 O           Me H  6-(2-CN-phenoxy)-pyrimidin-4-yl    91 O           Me H  2-pyridyl    92 CC          Me H  phenyl    93 CC          Me H  2-Me-phenyl    94 CC          Me H  3-Me-phenyl    95 CC          Me H  4-Me-phenyl    96 CC          Me H  2-Cl-phenyl    97 CC          Me H  2,5-Me.sub.2 -phenyl    98        ##STR52##  Me H  phenyl    99        ##STR53##  Me H  2-Me-phenyl    100        ##STR54##  Me H  3-Me-phenyl    101        ##STR55##  Me H  4-Me-phenyl    102        ##STR56##  Me H  2-Cl-phenyl    103        ##STR57##  Me H  3-Cl-phenyl    104        ##STR58##  Me H  4-Cl-phenyl    104        ##STR59##  Me H  2-F-phenyl    105        ##STR60##  Me H  3-F-phenyl    106        ##STR61##  Me H  4-F-phenyl    107        ##STR62##  Me H  2-Br-phenyl    108        ##STR63##  Me H  3-Br-phenyl    109        ##STR64##  Me H  4-Br-phenyl    110        ##STR65##  Me H  2-CF.sub.3 -phenyl    111        ##STR66##  Me H  3-CF.sub.3 -phenyl    112        ##STR67##  Me H  4-CF.sub.3 -phenyl    113        ##STR68##  Me H  2-OCH.sub.3 -phenyl    114        ##STR69##  Me H  3-OCH.sub.3 -phenyl    115        ##STR70##  Me H  4-OCH.sub.3 -phenyl    116        ##STR71##  Me H  2-CO.sub.2 Me-phenyl    117        ##STR72##  Me H  3-CO.sub.2 Me-phenyl    118        ##STR73##  Me H  4-CO.sub.2 Me-phenyl    119        ##STR74##  Me H  2,3-Me.sub.2 -phenyl    120        ##STR75##  Me H  2,4-Me.sub.2 -phenyl    121        ##STR76##  Me H  2,5-Me.sub.2 -phenyl    122        ##STR77##  Me H  2,6-Me.sub.2 -phenyl    123        ##STR78##  Me H  3,4-Me.sub.2 -phenyl    124        ##STR79##  Me H  3,5-Me.sub.2 -phenyl    125        ##STR80##  Me H  2,3-Cl.sub.2 -phenyl    126        ##STR81##  Me H  2,4-Cl.sub.2 -phenyl    127        ##STR82##  Me H  2,5-Cl.sub.2 -phenyl    128        ##STR83##  Me H  2,6-Cl.sub.2 -phenyl    129        ##STR84##  Me H  3,4-Cl.sub.2 -phenyl    130        ##STR85##  Me H  3,5-Cl.sub.2 -phenyl    131        ##STR86##  Me H  2-Cl-, 4-Me-phenyl    132        ##STR87##  Me H  2-Cl-, 5-Me-phenyl    133        ##STR88##  Me H  2-Me-, 4-Cl-phenyl    134        ##STR89##  Me H  2-Me-, 5-Cl-phenyl    135        ##STR90##  Me H  2-pyridyl    136        ##STR91##  Me H  2-naphthyl    137        ##STR92##  Me H  1-Me-2-naphthyl    138        ##STR93##  Me H  2-furyl    139       CH.sub.2O   Me Me phenyl    140       CH.sub.2O   Et H  phenyl    141       CH.sub.2O   Et Et phenyl    __________________________________________________________________________

The novel compounds are suitable as fungicides, insecticides andnematocides.

The active ingredients according to the invention, or agents containingthem, may be applied for instance in the form of directly sprayablesolutions, powders, suspensions (including high-percentage aqueous, oilyor Other suspensions), dispersions, emulsions, oil dispersions, pastes,dusts, broadcasting agents, or granules by spraying, atomizing, dusting,broadcasting or watering. The forms of application depend entirely onthe purpose for which the agents are being used, but they must ensure asfine a distribution of the active ingredients according to the inventionas possible.

Normally, the plants are sprayed or dusted with the active ingredientsor the seeds of the plants are treated with the active ingredients.

The formulations are produced in known manner, for example by extendingthe active ingredient With solvents and/or carriers, with or without theuse of emulsifiers and dispersants; if water is used as solvent, it isalso possible to employ other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are solvents such as aromatics(e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins(e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones(e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide),and water; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfiteWaste liquors and methylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, Wood meal, and nutshell meal,cellulosic powders, etc.

Examples of such formulations are given below.

I. A solution of 90 parts by weight of compound 2 from Table 1 and 10parts by weight of N-methyl-α-pyrrolidone, which is suitable forapplication in the form of very fine drops.

II. A mixture of 20 parts by weight of compound 25 from Table 1, 80parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil. By finely dispersing the mixture in water, a dispersionis obtained.

III. An aqueous dispersion of 20 parts by weight of compound 54 fromTable-1, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound 130 fromTable 1, 25 parts by weight of cyclohexanol, 65 parts by weight of amineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of compound 2 fromTable 1, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and7 parts by weight of powdered silica gel. By finely dispersing themixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound 25 from Table 1and 97 parts by weight of particulate kaolin. The dust contains 3 wt% ofthe active ingredient.

VII. An intimate mixture of 30 parts by weight of compound 54 from Table1, 92 parts by weight of powdered silica gel and 8 parts by weight ofparaffin oil Sprayed onto the surface of this silica gel. Thisformulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound 130from Table 1, 10 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound 2 fromTable 1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonicacid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts byweight of the sodium salt of a phenolsulfonic acid-urea-formaldehydecondensate and 68 parts by weight of a paraffinic mineral oil.

The novel compounds are extremely effective on a broad spectrum ofphytopathogenic fungi, in particular those from the class consisting ofthe Ascomycetes and Basidiomycetes. Some of them have systemic mobilityand action after application to the soil and foliage.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially-wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, grapevines, fruit and ornamentals, and in vegetables such ascucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials orsoil to be protected against fungus attack with a fungicidally effectiveamount of the active ingredients. The compounds may be applied before orafter infection of the materials, plants or seeds by the fungi.

The compounds I are particularly useful for controlling the followingplant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in Strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compounds may also be used for protecting materials (timber),for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt% of active ingredient.

The application rates depend on the type of effect desired, but aregenerally from 0.02 to 3 kg of active ingredient per hectare.

When the active ingredients are used for treating seed, applicationrates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg ofseed are generally required.

When the agents according to the invention are used as fungicides, theymay be employed together with other active ingredients, e.g.,herbicides, insecticides, growth regulators, other fungicides andfertilizers.

Use Example 1

Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results of the experiment show that compounds nos. 2, 25 and 54 fromTable I, when applied as spray liquors containing 63 ppm of activeingredient, have a very good fungicidal action (0% attack).

Use Example 2

Action on Botrytis cinerea in paprika

Slices of green paprika pods were sprayed to runoff with aqueousformulations containing (dry basis) 80% of active ingredient and 20% ofemulsifier. Two hours after the sprayed-on layer had dried, the sliceswere inoculated with a spore suspension of Botrytis cinerea whichcontained 1.7×10⁶ spores per ml of a 2% strength biomalt solution. Theinoculated slices were then incubated for 4 days in moist chambers.Botrytis spread on the slices was then assessed visually.

The results show that compounds nos. 2, 25 and 54 from Table I, whenapplied as spray liquors containing 500 ppm of active ingredient, have avery good fungicidal action (5% attack).

We claim:
 1. A thioamide of the formula I, ##STR94## where A and B areidentical or different and each is hydrogen, C₁₋₄ -alkyl, C₁₋₄ -alkoxyor halogen;X is ═CHCH₃ ; R¹ and R² are hydrogen or C₁₋₄ alkyl; Y is--CH₂ --O--; and R is a phenyl with at least one substituent selectedfrom the group consisting of nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkyl, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy,benzyloxy; with the proviso that at least one substituent is always C₁-C₄ -alkoximino-C₁ -C₄ -alkyl.